CN117247508A - Comb-structured long-chain polyamide and preparation method thereof - Google Patents
Comb-structured long-chain polyamide and preparation method thereof Download PDFInfo
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- CN117247508A CN117247508A CN202311104442.6A CN202311104442A CN117247508A CN 117247508 A CN117247508 A CN 117247508A CN 202311104442 A CN202311104442 A CN 202311104442A CN 117247508 A CN117247508 A CN 117247508A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 67
- 229920002647 polyamide Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 239000000243 solution Substances 0.000 claims abstract description 116
- 229920001778 nylon Polymers 0.000 claims abstract description 92
- 239000004677 Nylon Substances 0.000 claims abstract description 84
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 238000007112 amidation reaction Methods 0.000 claims abstract description 5
- 239000002981 blocking agent Substances 0.000 claims abstract description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 10
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 229940005605 valeric acid Drugs 0.000 claims description 7
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 6
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 claims description 4
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 4
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- IDSLBLWCPSAZBL-UHFFFAOYSA-N 2-cyanopropan-2-yl benzenecarbodithioate Chemical compound N#CC(C)(C)SC(=S)C1=CC=CC=C1 IDSLBLWCPSAZBL-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000000071 blow moulding Methods 0.000 claims description 2
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims description 2
- JGHKDVSIFPFNIJ-UHFFFAOYSA-N dodecylsulfanylmethanedithioic acid Chemical compound CCCCCCCCCCCCSC(S)=S JGHKDVSIFPFNIJ-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 238000002074 melt spinning Methods 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- 229940117803 phenethylamine Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000012989 trithiocarbonate Substances 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 27
- 238000009826 distribution Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000010526 radical polymerization reaction Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 238000013467 fragmentation Methods 0.000 description 6
- 238000006062 fragmentation reaction Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 229920006122 polyamide resin Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Abstract
The invention relates to a comb-structured long-chain polyamide and a preparation method thereof, wherein the preparation method comprises the following steps: s1, providing a nylon salt solution, adding a blocking agent into the nylon salt solution, and uniformly mixing to obtain a reaction solution A; s2, carrying out polycondensation reaction on the reaction liquid A to obtain a polyamide prepolymer melt; s3, dissolving the polyamide prepolymer melt in the solvent A, adding acrylic acid and a catalyst, mixing to obtain a reaction solution B, and carrying out amidation reaction on the reaction solution B to obtain a long-chain nylon prepolymer AA-LCPA; s4, adding the AA-LCPA, the polythioester chain transfer agent and the initiator into the solvent B, uniformly mixing to obtain a reaction solution C, and carrying out RAFT polymerization reaction on the reaction solution C to obtain a polymer solution; s5, dropwise adding the polymer solution into a methanol solution, filtering, washing and drying to obtain the comb-structured long-chain polyamide. The long-chain polyamide synthesized by the invention has a comb-shaped structure, and has more excellent mechanical properties and good fluidity.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to comb-structured long-chain polyamide and a preparation method thereof.
Background
Polyamide resin, commonly called nylon, has excellent mechanical properties, excellent barrier properties, high heat resistance, high wear resistance, high chemical corrosion resistance and other excellent comprehensive properties, and is widely applied to the fields of mechanical manufacturing industry, electric tools, electronic appliances, transportation and the like. In nylon molecules, nylon with the methylene length between 2 amide groups of more than 10 is generally called as long carbon chain nylon, and the nylon has the characteristics of good toughness and softness, low water absorption, good dimensional stability, excellent dielectric property, good wear resistance, low density and the like besides the characteristics of most of common properties of common nylon such as lubricity, wear resistance and compression resistance, easy processing and the like, and is widely applied.
The molecular weight distribution index is defined as the ratio of the weight average molecular weight to the number average molecular weight, and has the physical meaning that the narrower the molecular weight distribution index is, the molecular weight of each molecular chain of the polymer tends to be the same, and the chain length is the same, otherwise, the larger the chain length difference among the molecular chains of the polymer is, and the molecular weight is different. In some special fields, such as the field of pipes, nylon resins are required to have a higher molecular weight, which maintains good mechanical properties, heat resistance, abrasion resistance, corrosion resistance, etc., but at the same time is also required to have good flowability, or a larger molecular weight means more excellent properties under the condition of uniform flowability (uniform processability). Compared with a polymer with narrow PDI, a polymer with wider molecular weight distribution has larger and smaller molecules due to uneven chain length, wherein the low polymer with small molecular content and the precipitation of the small molecules are common problems in nylon material application, especially in the field of electronic and electric appliances, as the low polymer small molecules are contained in electronic components prepared from the nylon material, the low polymer small molecules are easy to migrate and precipitate and have corrosion effect on contacted metal devices, and the service life of equipment is reduced. In addition, the uneven molecular weight distribution causes uneven action among polymer chains, and also affects the overall mechanical properties of the polymer.
At present, long-chain nylon in the market such as PA610, PA612, PA1012, PA11, PA12 and the like are all long-chain linear structures, and the polymerization method is one-step polymerization of diamine and dibasic acid salification post-polycondensation. From the prior art, for long-chain nylon polymerization, the processes of temperature rise, pressure maintaining, pressure reduction and vacuum pumping are adopted, the molecular weight rise is mainly in the high-temperature vacuum pumping stage, and under the condition of short-time high vacuum, side reactions are more, firstly, the color forming and ring forming reaction are easy to generate in the stage, the color of the polymer is caused, and secondly, the local polymerization is very easy to cause too fast, so that the molecular weight distribution of the polymer obtained by the process is not narrow enough, and further application of the polymer in the special field is influenced.
Disclosure of Invention
Based on the above, aiming at the technical problems that the molecular weight distribution of the obtained polymer is not narrow enough to influence the further application of the polymer in the special field in the prior art adopting the processes of temperature rise, pressure maintaining, pressure reduction and vacuum pumping for long-chain nylon polymerization, the invention needs to provide a comb-structured long-chain polyamide and a preparation method thereof, and the obtained polymer has more excellent performance compared with the long-chain polyamide with the same composition due to the difference of the structure and the polymerization method, and is suitable for industrial production.
The invention provides a preparation method of comb-structured long-chain polyamide, which comprises the following steps:
s1, providing a nylon salt solution, adding a blocking agent into the nylon salt solution, and uniformly mixing to obtain a reaction solution A;
s2, carrying out polycondensation reaction on the reaction liquid A to obtain a polyamide prepolymer melt with one end blocked by carboxyl;
s3, dissolving the polyamide prepolymer melt in the solvent A, adding acrylic acid and a catalyst, mixing to obtain a reaction solution B, and carrying out amidation reaction on the reaction solution B to obtain a long-chain nylon prepolymer AA-LCPA with one end being acrylic acid;
s4, adding the AA-LCPA, the polythioester chain transfer agent and the initiator into the solvent B, uniformly mixing to obtain a reaction solution C, and carrying out RAFT polymerization reaction on the reaction solution C to obtain a polymer solution;
s5, dropwise adding the polymer solution into a methanol solution, filtering, washing and drying to obtain the comb-structured long-chain polyamide.
Compared with the common linear chain nylon, the long chain polyamide prepared by the invention has a comb-shaped structure, can effectively reduce the viscosity of the fluid and increase the volume weight ratio of the polymer due to the branching of the structure, has more excellent mechanical property and good fluidity under the same molecular weight condition, is very suitable for application fields with higher requirements on molecular weight but certain requirements on fluidity, such as the field of pipe extrusion, has extremely narrow molecular weight distribution and more excellent thermodynamic property, and solves the technical problems that the molecular weight distribution of the polymer obtained by the technology of temperature rise, pressure maintaining, pressure reduction and vacuum pumping is not narrow enough and further application in the special field is influenced.
As a further improvement of the above scheme, in the step S1, the preparation process of the nylon salt solution is as follows: and (3) under the inert atmosphere, adding diamine and long-chain dibasic acid into water, uniformly mixing, adjusting the pH to 6.5-8.2, adding a stabilizer, and uniformly mixing to obtain the nylon salt solution.
As a further improvement of the scheme, the mass concentration of the nylon salt in the nylon salt solution is 40% -75%;
and/or the reaction liquid A comprises the following raw materials in parts by mole: 0.1-100 parts of diamine, 0.1-100 parts of long carbon chain dibasic acid, 0.001-0.1 part of stabilizer and 0.001-5 parts of end capping agent; preferably, the reaction solution A comprises the following raw materials in parts by mole: 0-40 parts of diamine, 85-100 parts of long carbon chain dibasic acid, 0.005-0.05 part of stabilizer and 0.001-2 parts of end capping agent;
and/or diamine is at least one of pentanediamine, hexanediamine, decanediamine and dodecanediamine;
and/or the long carbon chain diacid is at least one of diacid, undecanediacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid; preferably, the long carbon chain diacid is at least one of sebacic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid and hexadecanedioic acid;
and/or the stabilizer is at least one of phosphorous acid, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite and potassium hypophosphite;
and/or the end capping agent is at least one of 1-ethylamine, 1-propylamine, 1-butylamine, 1-pentylamine, benzylamine and phenethylamine
As a further improvement of the above scheme, in the step S2, the polycondensation process of the reaction liquid a is: heating the reaction solution A to increase the pressure in the reaction system to 0.3-3.2MPa, exhausting and maintaining the pressure, and reducing the pressure to normal pressure and continuing the reaction under the normal pressure when the temperature of the system is increased to 230-260 ℃.
As a further improvement of the above-mentioned scheme, in the step S3, the polyamide prepolymer melt is dissolved in a homogeneous solution formed after the solvent a, and the mass concentration of the polyamide prepolymer melt is in the range of 20% to 60%;
and/or, in the step S3, the amidation reaction process of the reaction liquid B is: heating the reaction liquid B to 120-160 ℃ and carrying out constant-temperature reaction at the temperature, and slowly reducing the pressure to normal pressure within 0.5-2h of the reaction.
As a further improvement of the above scheme, in the step S3, the catalyst is at least one of phosphorous acid, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite, and potassium hypophosphite;
and/or, in the step S3, the solvent a is one of tetrahydrofuran, acetone, and cyclohexanone;
and/or in the step S3, 1-30 parts of acrylic acid and 0.001-0.1 part of catalyst are included in the reaction liquid B in terms of mole parts.
As a further improvement of the above scheme, in the step S4, the polythioester chain transfer agent is at least one of cyanoisopropyl dithiobenzoate, 4-cyano-4-dithiobenzoyloxy valeric acid, 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 2- (dodecyl trithiocarbonate) -2-isobutyric acid, 4-cyano-4-lauryl trithiocarbonate;
and/or in the step S4, the initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutylvaleric acid, dibenzoyl peroxide, cyclohexanone peroxide and tert-butyl hydroperoxide;
and/or, in the step S4, the solvent B is one of tetrahydrofuran, acetone, and cyclohexanone;
and/or in the step S4, 0.1-10 parts of polythioester chain transfer agent and 0.01-2 parts of initiator are included in the reaction liquid C by mol parts. Preferably, the polythioester chain transfer agent is 0.2 to 5 parts.
As a further improvement of the above-described scheme, in the step S5, the mass of the methanol solution is 5 to 10 times the mass of the polymer solution.
The invention also provides a comb-structured long-chain polyamide which is prepared by adopting the preparation method.
The invention also provides a polyamide molding product, which is obtained by adopting the long-chain polyamide with the comb structure through a molding method, wherein the molding method is at least one selected from injection molding, extrusion molding, blow molding, vacuum molding, melt spinning and film molding.
Compared with the prior art, the invention has the following beneficial effects:
1. the long-chain polyamide synthesized by the invention has a comb-shaped structure, can effectively reduce the viscosity of fluid and increase the volume weight ratio of polymer due to the branching of the structure, has more excellent mechanical property and good fluidity under the same molecular weight condition compared with common nylon with a straight-chain structure, and is very suitable for application fields with higher molecular weight requirements but certain requirements on fluidity, such as pipe extrusion fields, and has extremely narrow molecular weight distribution and more excellent thermodynamic property.
2. The invention adopts RAFT polymerization mode to prepare comb long chain nylon, reversible-addition-fragmentation chain transfer (RAFT) polymerization is an excellent activity-control polymerization method, can effectively synthesize low molecular weight distribution polymer, can accurately obtain target molecular weight polymer through adjusting reaction conditions, can ensure narrow molecular weight distribution, has simple reaction steps and mild reaction conditions, and the prepared long chain nylon has narrow molecular weight distribution index and excellent mechanical properties.
3. The preparation method provided by the invention avoids the problem that the traditional preparation processes such as high temperature and high pressure, vacuumizing and the like are easy to cause chromogenic reaction, and simultaneously can effectively dissolve and remove chromogenic substances in the final precipitation stage, so that the prepared long-chain nylon has a very low yellow index, and has better application in some natural-color workpieces and appearance workpieces.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying tables in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a comb-structured long-chain polyamide, and the preparation method comprises the following five steps S1-S5.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of sebacic acid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight percent of 50. The prepared nylon salt solution was adjusted to pH 7.60 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, adding 0.008mol of end-capping agent 2-ethylamine, and stirring and mixing uniformly to obtain a reaction solution A1.
S2, heating the reaction solution A1 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting, maintaining the pressure at 1.30MPa, and the temperature of the reaction system at 230 ℃ at the end of the pressure maintaining time is 3 hours. Then, the pressure in the reaction system was reduced to 0MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 240℃and the time for depressurization was 1.5 hours. And (3) continuing the normal pressure reaction for 20min after the depressurization is finished, and obtaining a polyamide prepolymer melt with one end blocked by carboxyl groups (one end blocked and the other end provided with amino groups).
S3, dissolving a polyamide prepolymer melt with one end blocked by carboxyl into a cyclohexanone solution to form a uniform solution with the mass fraction of 35%, adding 0.5mol of acrylic acid and 0.001mol of calcium hypophosphite, and uniformly mixing to obtain a reaction solution B1. Heating the reaction solution B1 to about 120-160 ℃, reacting at the constant temperature for a period of time, slowly reducing the pressure within 0.5-2h of the reaction, discharging the solvent and the reaction water, and reducing the pressure to normal pressure to obtain the long-chain nylon prepolymer AA-LCPA powder with the acrylic acid at one end.
S4, adding AA-LCPA powder, 0.05mol of 4-cyano-4-dithiobenzoyloxy valeric acid and 0.001mol of initiator azobisisobutyronitrile into cyclohexanone solution, uniformly mixing to obtain 35% wt of reaction solution C, and carrying out reversible-addition-fragmentation chain transfer active radical polymerization (RAFT polymerization, namely initiating acrylic acid to carry out active radical polymerization) on the reaction solution C at 90 ℃ for 12 hours to obtain a polymer solution.
S5, dropwise adding the polymer solution into methanol solution with the mass being 5 times that of the polymer solution, separating out long-chain nylon polymer solids, filtering to obtain solids, and washing and drying the solids to obtain the comb-structured long-chain polyamide.
Example 2
The embodiment provides a comb-structured long-chain polyamide, and the preparation method comprises the following five steps S1-S5.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of sebacic acid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight percent of 50. The prepared nylon salt solution was adjusted to pH 7.60 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, adding 0.006mol of end capping agent 2-ethylamine, and stirring and mixing uniformly to obtain a reaction solution A2.
S2, heating the reaction solution A2 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting, maintaining the pressure at 1.30MPa, and the temperature of the reaction system at 230 ℃ at the end of the pressure maintaining time is 3 hours. Then, the pressure in the reaction system was reduced to 0MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 240℃and the time for depressurization was 1.5 hours. And (3) continuing the normal pressure reaction for 20min after the depressurization is finished, and obtaining a polyamide prepolymer melt with one end blocked by carboxyl groups (one end blocked and the other end provided with amino groups).
S3, dissolving a polyamide prepolymer melt with one end blocked by carboxyl into a cyclohexanone solution to form a uniform solution with the mass fraction of 35%, adding 0.5mol of acrylic acid and 0.001mol of calcium hypophosphite, and uniformly mixing to obtain a reaction solution B2. Heating the reaction solution B2 to about 120-160 ℃, reacting at the constant temperature for a period of time, slowly reducing the pressure within 0.5-2h of the reaction, discharging the solvent and the reaction water, and reducing the pressure to normal pressure to obtain the long-chain nylon prepolymer AA-LCPA powder with the acrylic acid at one end.
S4, adding AA-LCPA powder, 0.05mol of 4-cyano-4-dithiobenzoyloxy valeric acid and 0.001mol of initiator azobisisobutyronitrile into cyclohexanone solution, uniformly mixing to obtain 35% wt of reaction solution C2, and carrying out reversible-addition-fragmentation chain transfer active radical polymerization (RAFT polymerization, namely initiating acrylic acid to carry out active radical polymerization) on the reaction solution C2 at 90 ℃ for 12 hours to obtain a polymer solution.
S5, dropwise adding the polymer solution into methanol solution with the mass being 5 times that of the polymer solution, separating out long-chain nylon polymer solids, filtering to obtain solids, and washing and drying the solids to obtain the comb-structured long-chain polyamide.
Example 3
The embodiment provides a comb-structured long-chain polyamide, and the preparation method comprises the following five steps S1-S5.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of dodecadiacid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight of 50%. The prepared nylon salt solution was adjusted to pH 7.60 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, adding 0.008mol of end-capping agent 2-ethylamine, and stirring and mixing uniformly to obtain a reaction solution A3.
S2, heating the reaction solution A3 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting, maintaining the pressure at 1.30MPa, and the temperature of the reaction system at 230 ℃ at the end of the pressure maintaining time is 3 hours. Then, the pressure in the reaction system was reduced to 0MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 240℃and the time for depressurization was 1.5 hours. And (3) continuing the normal pressure reaction for 20min after the depressurization is finished, and obtaining a polyamide prepolymer melt with one end blocked by carboxyl groups (one end blocked and the other end provided with amino groups).
S3, dissolving a polyamide prepolymer melt with one end blocked by carboxyl into a cyclohexanone solution to form a uniform solution with the mass fraction of 35%, adding 0.5mol of acrylic acid and 0.001mol of calcium hypophosphite, and uniformly mixing to obtain a reaction solution B3. Heating the reaction solution B3 to about 120-160 ℃, reacting at the constant temperature for a period of time, slowly reducing the pressure within 0.5-2h of the reaction, discharging the solvent and the reaction water, and reducing the pressure to normal pressure to obtain the long-chain nylon prepolymer AA-LCPA powder with the acrylic acid at one end.
S4, adding AA-LCPA powder, 0.05mol of 4-cyano-4-dithiobenzoyloxy valeric acid and 0.001mol of initiator azobisisobutyronitrile into cyclohexanone solution, uniformly mixing to obtain 35% wt of reaction solution C3, and carrying out reversible-addition-fragmentation chain transfer active radical polymerization (RAFT polymerization, namely initiating acrylic acid to carry out active radical polymerization) on the reaction solution C3 at 90 ℃ for 12 hours to obtain a polymer solution.
S5, dropwise adding the polymer solution into methanol solution with the mass being 5 times that of the polymer solution, separating out long-chain nylon polymer solids, filtering to obtain solids, and washing and drying the solids to obtain the comb-structured long-chain polyamide.
Example 4
The embodiment provides a comb-structured long-chain polyamide, and the preparation method comprises the following five steps S1-S5.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of dodecadiacid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight of 50%. The prepared nylon salt solution was adjusted to pH 7.60 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, adding 0.006mol of end capping agent 2-ethylamine, and stirring and mixing uniformly to obtain a reaction solution A4.
S2, heating the reaction solution A4 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting, maintaining the pressure at 1.30MPa, and the temperature of the reaction system is 230 ℃ at the end of the pressure maintaining time for 3 hours. Then, the pressure in the reaction system was reduced to 0MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 240℃and the time for depressurization was 1.5 hours. And (3) continuing the normal pressure reaction for 20min after the depressurization is finished, and obtaining a polyamide prepolymer melt with one end blocked by carboxyl groups (one end blocked and the other end provided with amino groups).
S3, dissolving a polyamide prepolymer melt with one end blocked by carboxyl into a cyclohexanone solution to form a uniform solution with the mass fraction of 35%, adding 0.5mol of acrylic acid and 0.001mol of calcium hypophosphite, and uniformly mixing to obtain a reaction solution B4. Heating the reaction solution B4 to about 120-160 ℃, reacting at the constant temperature for a period of time, slowly reducing the pressure within 0.5-2h of the reaction, discharging the solvent and the reaction water, and reducing the pressure to normal pressure to obtain the long-chain nylon prepolymer AA-LCPA powder with the acrylic acid at one end.
S4, adding AA-LCPA powder, 0.05mol of 4-cyano-4-dithiobenzoyloxy valeric acid and 0.001mol of initiator azobisisobutyronitrile into cyclohexanone solution, uniformly mixing to obtain 35% wt of reaction solution C4, and carrying out reversible-addition-fragmentation chain transfer active radical polymerization (RAFT polymerization, namely initiating acrylic acid to carry out active radical polymerization) on the reaction solution C4 at 90 ℃ for 12 hours to obtain a polymer solution.
S5, dropwise adding the polymer solution into methanol solution with the mass being 5 times that of the polymer solution, separating out long-chain nylon polymer solids, filtering to obtain solids, and washing and drying the solids to obtain the comb-structured long-chain polyamide.
Comparative example 1
The comparative example provides a long-chain polyamide, the preparation method of which comprises the following four steps S1-S4.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of sebacic acid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight percent of 50. The prepared nylon salt solution was adjusted to pH 8.10 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, and stirring and mixing uniformly to obtain a reaction solution A5.
S2, heating the reaction solution A5 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting to maintain the pressure at 1.50MPa, and the temperature of the reaction system at the end of the pressure maintaining is 238 ℃ and the pressure maintaining time is 3 hours. Then, the pressure in the reaction system was reduced to 0.002MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 255℃and the depressurization took 1 hour.
S3, vacuumizing to-0.04 MPa at 255 ℃ after depressurization is finished, and continuing to react for 35min under normal pressure. .
S4, melting and discharging, cooling, bracing, granulating, and drying to obtain the linear long-chain nylon PA610 particles.
Comparative example 2
The comparative example provides a long-chain polyamide, the preparation method of which comprises the following four steps S1-S4.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of dodecadiacid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight of 50%. The prepared nylon salt solution was adjusted to pH 8.10 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, and stirring and mixing uniformly to obtain a reaction solution A6.
S2, heating the reaction solution A6 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting to maintain the pressure at 1.50MPa, and the temperature of the reaction system at the end of the pressure maintaining is 238 ℃ and the pressure maintaining time is 3 hours. Then, the pressure in the reaction system was reduced to 0.002MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 255℃and the depressurization took 1 hour.
S3, vacuumizing to-0.04 MPa at 255 ℃ after depressurization is finished, and continuing to react for 35min under normal pressure. .
S4, melting and discharging, cooling, bracing, granulating, and drying to obtain the linear long-chain nylon PA610 particles.
Comparative example 3
The comparative example provides a long-chain polyamide, the preparation method of which comprises the following five steps S1-S5.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of sebacic acid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight percent of 50. The prepared nylon salt solution was adjusted to pH 7.60 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, and stirring and mixing uniformly to obtain a reaction solution A6.
S2, heating the reaction solution A6 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting to maintain the pressure at 1.30MPa, and the temperature of the reaction system at the end of the pressure maintaining is 230 ℃ and the pressure maintaining time is 3 hours. Then, the pressure in the reaction system was reduced to 0MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 240℃and the time for depressurization was 1.5 hours. And after the depressurization is finished, continuing to react for 20 minutes at normal pressure at 240 ℃ to obtain an uncapped polyamide prepolymer melt.
S3, dissolving the melt of the unblocked polyamide prepolymer in a cyclohexanone solution to form a uniform solution with the mass fraction of 35%, adding 0.5mol of acrylic acid and 0.001mol of calcium hypophosphite, and uniformly mixing to obtain a reaction solution B4. Heating the reaction solution B4 to about 120-160 ℃, reacting at the constant temperature for a period of time, slowly reducing the pressure within 0.5-2h of the reaction, discharging the solvent and the reaction water, and reducing the pressure to normal pressure to obtain the long-chain nylon prepolymer AA-LCPA powder with the acrylic acid at one end.
S4, adding AA-LCPA powder, 0.05mol of 4-cyano-4-dithiobenzoyloxy valeric acid and 0.001mol of initiator azobisisobutyronitrile into cyclohexanone solution, uniformly mixing to obtain 35% wt of reaction solution C4, and carrying out reversible-addition-fragmentation chain transfer active radical polymerization (RAFT polymerization, namely initiating acrylic acid to carry out active radical polymerization) on the reaction solution C4 at 90 ℃ for 12 hours to obtain a polymer solution.
S5, dropwise adding the polymer solution into methanol solution with the mass being 5 times that of the polymer solution, separating out long-chain nylon polymer solids, filtering to obtain solids, and washing and drying the solids to obtain the comb-structured long-chain polyamide.
Comparative example 4
The comparative example provides a long-chain polyamide, the preparation method of which comprises the following five steps S1-S5.
S1, uniformly mixing 10mol of 1, 6-hexamethylenediamine, 10mol of sebacic acid and water under a nitrogen atmosphere to prepare a nylon salt solution with the weight percent of 50. The prepared nylon salt solution was adjusted to pH 7.60 with hexamethylenediamine. Then adding 0.001mol of sodium hypophosphite into the nylon salt solution, adding 0.008mol of end-capping agent 2-ethylamine, and stirring and mixing uniformly to obtain a reaction solution A4.
S2, heating the reaction solution A4 to enable the pressure in the reaction system to rise to 1.5MPa, wherein the pressure rising time is 1 hour and 30 minutes, exhausting, maintaining the pressure at 1.30MPa, and the temperature of the reaction system is 230 ℃ at the end of the pressure maintaining time for 3 hours. Then, the pressure in the reaction system was reduced to 0MPa (gauge pressure) by depressurization, and after the completion of the depressurization, the temperature of the reaction system was 240℃and the time for depressurization was 1.5 hours. And (3) continuing the normal pressure reaction for 20min after the depressurization is finished, and obtaining a polyamide prepolymer melt with one end blocked by carboxyl groups (one end blocked and the other end provided with amino groups).
S3, dissolving a polyamide prepolymer melt with one end blocked by carboxyl into a cyclohexanone solution to form a uniform solution with the mass fraction of 35%, adding 0.5mol of acrylic acid and 0.001mol of calcium hypophosphite, and uniformly mixing to obtain a reaction solution B4. Heating the reaction solution B4 to about 120-160 ℃, reacting at the constant temperature for a period of time, slowly reducing the pressure within 0.5-2h of the reaction, discharging the solvent and the reaction water, and reducing the pressure to normal pressure to obtain the long-chain nylon prepolymer AA-LCPA powder with the acrylic acid at one end.
S4, adding AA-LCPA powder and 0.001mol of initiator azodiisobutyronitrile into cyclohexanone solution, uniformly mixing to obtain 35%wt of reaction solution C4, and carrying out ordinary free radical polymerization on the reaction solution C4 at 90 ℃ for 12 hours to obtain a polymer solution.
S5, dropwise adding the polymer solution into methanol solution with the mass being 5 times that of the polymer solution, separating out long-chain nylon polymer solids, filtering to obtain solids, and washing and drying the solids to obtain the comb-structured long-chain polyamide.
Test case
The measurement of this test example was performed under the following conditions.
A detector: RI detector.
Chromatographic column: 2x PSS 7 μ PFG Linear M column 300x 8.0mm, solvent: hexafluoroisopropanol containing sodium trifluoroacetate at a concentration of 0.05 mol/L.
Temperature: 40 ℃.
Flow rate: 1mL/min.
Injection amount: 100. Mu.L.
Concentration: 3-5 g/L.
Sample preparation: the polyamide resin or the polyamide resin composition obtained in each example was weighed in 0.01 mol/L hexafluoroisopropanol containing sodium trifluoroacetate so as to convert the polyamide resin into 0.5mg/mL, and stirred at room temperature for 1 hour to dissolve, and the obtained solution was filtered by a hydrophobic membrane filter (pore size 0.22 μm) to prepare a sample.
PMMA standard sample: a STANDARD elution curve (calibration curve) was prepared using STANDARD81506-1EA (number average molecular weight range: 500-27000000) prepared by Fluka.
Yellow index test (YI value): reference standard: ASTM D:1925 Table 1 performance test.
The long-chain polyamides prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to melt index test, yellow index test, and then mechanical test with reference to standard ISO-572; impact performance testing was performed with reference to standard ISO-180/1A; and molecular weight testing by GPC, the results of which are shown in Table 1.
TABLE 1
From the results in Table 1, it can be seen that:
1. as can be seen from comparative examples 1 and 1, for the long-chain nylon PA610, the mechanical properties are substantially the same under the condition of equivalent molecular weight, but the melt index of example 1 is 8.1g/10min, and the melt index of comparative example 1 is 5.2g/10min, because the long-chain nylon prepared in example 1 has a comb-type structure, the flowability is improved by about 56%, and in some application fields such as the pipe field, the extrusion speed, i.e. the productivity, can be improved rapidly, the processability is improved greatly, and it is well known that the polymer molecular weight and the mechanical properties are greatly correlated, and that the long-chain nylon PA of example 1 and comparative example 1 have better tensile strength, bending strength and impact strength in the future under the same molecular weight condition because the long-chain nylon PA of example 1 has narrower molecular weight distribution.
2. It can be seen from example 2 and comparative example 1 that the melt fingers are substantially consistent under the condition of comparable flow properties, and at the same time, the long-chain nylon prepared in example 2 has a molecular weight of 36400, which is about 14% higher than the molecular weight 27600 of the long-chain nylon prepared in comparative example 1, and that the long-chain nylon prepared in example 2 has a tensile strength of 14% higher than the long-chain nylon prepared in comparative example 1, a flexural strength of 12% higher than the flexural strength of 9% higher than the flexural strength, and that the PA610 of comb-type structure having a low molecular weight distribution index has more excellent mechanical properties under the same processing conditions, i.e., flowability.
3. As can be seen from comparative examples 3 and 2, the mechanical properties of the long-chain nylon PA612 are basically the same under the condition of equivalent molecular weight, but the melt index of the long-chain nylon prepared in example 3 is 7.6g/10min, and the long-chain nylon prepared in comparative example 2 is 5.3g/10min, and the flow property of the long-chain nylon prepared in example 3 is improved by about 43% due to the comb structure, so that the extrusion speed, namely the productivity, can be improved rapidly in some application fields such as the pipe field, and the processing property of the long-chain nylon is improved greatly. Meanwhile, example 3 has better tensile strength, flexural strength, and impact strength than comparative example 2 in the present period because example 3 has a narrower molecular weight distribution under the same molecular weight conditions.
4. It can be seen from example 4 and comparative example 2 that the melt index is substantially uniform under the condition that the flow properties are equivalent, and that the molecular weight of the long-chain nylon prepared in example 4 is 45100, which is about 32% higher than the molecular weight 34200 of the long-chain nylon prepared in comparative example 2 due to the comb-shaped structure, and that the tensile strength of the long-chain nylon prepared in example 4 is 17% higher, the flexural strength is 9% higher, and the impact strength is 2% higher than the long-chain nylon prepared in comparative example 2 due to the macroscopic properties, and that the PA612 having a comb-shaped structure with a low molecular weight distribution index has more excellent mechanical properties under the same processing conditions, i.e., flowability.
5. Comparative examples 1-4 and comparative examples 1-2, the long chain nylons prepared in examples 1-4 were found to have a yellowness index of about 1.2, which is significantly lower than about 3-4 of the long chain nylons prepared in comparative examples, indicating that the polyamides prepared by the process of the present invention have a better appearance than the polyamides prepared by conventional processes.
6. As can be seen from comparative example 4 of comparative example 3 of example 1, the molecular weight is not controlled when there is no end-capping agent, resulting in an excessively large molecular weight of the final polymer, with a melt index of 0.7g/10min, which is very difficult to process, has a very high viscosity, and cannot be processed at all in the relevant fields; therefore, the end capping agent is necessary to regulate and control the molecular weight and the end groups, thereby achieving effective control of the molecular weight.
7. When no chain transfer agent is added from comparative example 4 of example 1, the acrylic double bond at the end of the polyamide prepolymer has no means to carry out living radical polymerization, and the polymerization mechanism is general uncontrollable radical polymerization (i.e., molecular weight and molecular weight distribution are uncontrollable), so that the molecular chain of the polymer is excessively large, the melt index is 0.1g/10min, which is very difficult to process, has very large viscosity, and cannot be processed and used in the related field at all.
In summary, compared with common linear chain nylon with the same composition, the comb-type long polyamide prepared by the active free radical polymerization method has a comb-type structure, and has the advantages of narrow molecular weight distribution index, low yellow index, branching of the structure, lower fluid viscosity under the same molecular weight condition, larger weight-to-volume ratio of the polymer, excellent mechanical property and melt flow property, and wide application prospect in the field of pipes.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "or/and" as used herein includes any and all combinations of one or more of the associated listed items.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the comb-structured long-chain polyamide is characterized by comprising the following steps of:
s1, providing a nylon salt solution, adding a blocking agent into the nylon salt solution, and uniformly mixing to obtain a reaction solution A;
s2, carrying out polycondensation reaction on the reaction liquid A to obtain a polyamide prepolymer melt with one end blocked by carboxyl;
s3, dissolving the polyamide prepolymer melt in the solvent A, adding acrylic acid and a catalyst, mixing to obtain a reaction solution B, and carrying out amidation reaction on the reaction solution B to obtain a long-chain nylon prepolymer AA-LCPA with one end being acrylic acid;
s4, adding the AA-LCPA, the polythioester chain transfer agent and the initiator into the solvent B, uniformly mixing to obtain a reaction solution C, and carrying out RAFT polymerization reaction on the reaction solution C to obtain a polymer solution;
s5, dropwise adding the polymer solution into a methanol solution, filtering, washing and drying to obtain the comb-structured long-chain polyamide.
2. The method for preparing comb-structured long-chain polyamide according to claim 1, wherein in said step S1, the preparation process of the nylon salt solution is: and (3) under the inert atmosphere, adding diamine and long-chain dibasic acid into water, uniformly mixing, adjusting the pH to 6.5-8.2, adding a stabilizer, and uniformly mixing to obtain the nylon salt solution.
3. The method for preparing comb-structured long-chain polyamide according to claim 2, wherein the mass concentration of nylon salt in the nylon salt solution is 40% -75%;
and/or the reaction liquid A comprises the following raw materials in parts by mole: 0.1-100 parts of diamine, 0.1-100 parts of long carbon chain dibasic acid, 0.001-0.1 part of stabilizer and 0.001-5 parts of end capping agent;
and/or diamine is at least one of pentanediamine, hexanediamine, decanediamine and dodecanediamine;
and/or the long carbon chain diacid is at least one of diacid, undecanediacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid;
and/or the stabilizer is at least one of phosphorous acid, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite and potassium hypophosphite;
and/or the end capping agent is at least one of 1-ethylamine, 1-propylamine, 1-butylamine, 1-pentylamine, benzylamine and phenethylamine.
4. The method for preparing a comb-structured long-chain polyamide according to claim 1, wherein in said step S2, the polycondensation reaction process of said reaction liquid a is: heating the reaction solution A to increase the pressure in the reaction system to 0.3-3.2MPa, exhausting and maintaining the pressure, and reducing the pressure to normal pressure and continuing the reaction under the normal pressure when the temperature of the system is increased to 230-260 ℃.
5. The method for producing a comb-structured long-chain polyamide according to claim 1, wherein in said step S3, the concentration of the homogeneous solution formed by dissolving said polyamide prepolymer melt in the solvent a is in the range of 20% to 60%;
and/or, in the step S3, the amidation reaction process of the reaction liquid B is: heating the reaction liquid B to 120-160 ℃ and carrying out constant-temperature reaction at the temperature, and slowly reducing the pressure to normal pressure within 0.5-2h of the reaction.
6. The method for producing a comb-structured long-chain polyamide according to claim 1, wherein in the step S3, the catalyst is at least one of phosphorous acid, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite, and potassium hypophosphite;
and/or, in the step S3, the solvent a is one of tetrahydrofuran, acetone, and cyclohexanone;
and/or in the step S3, 1-30 parts of acrylic acid and 0.001-0.1 part of catalyst are included in the reaction liquid B in terms of mole parts.
7. The method for producing a comb-structured long-chain polyamide according to claim 1, wherein in the step S4, the polythioester chain transfer agent is at least one of cyanoisopropyl dithiobenzoate, 4-cyano-4-dithiobenzoyloxy valeric acid, 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 2- (dodecyl trithiocarbonate) -2-isobutyric acid, 4-cyano-4-lauryl trithiocarbonate;
and/or in the step S4, the initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutylvaleric acid, dibenzoyl peroxide, cyclohexanone peroxide and tert-butyl hydroperoxide;
and/or, in the step S4, the solvent B is one of tetrahydrofuran, acetone, and cyclohexanone;
and/or in the step S4, 0.1-10 parts of polythioester chain transfer agent and 0.01-2 parts of initiator are included in the reaction liquid C by mol parts.
8. The method for producing a comb-structured long-chain polyamide according to claim 1, wherein in said step S5, the mass of said methanol solution is 5 to 10 times the mass of said polymer solution.
9. A comb-structured long-chain polyamide, characterized in that it is produced by the production process according to any one of claims 1 to 8.
10. A polyamide molding obtained by a molding method using the comb-structured long-chain polyamide according to claim 9, wherein the molding method is at least one selected from the group consisting of injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, and film molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202311104442.6A CN117247508A (en) | 2023-08-30 | 2023-08-30 | Comb-structured long-chain polyamide and preparation method thereof |
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| CN202311104442.6A CN117247508A (en) | 2023-08-30 | 2023-08-30 | Comb-structured long-chain polyamide and preparation method thereof |
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